WO1994011099A1 - Emulsions aqueuses stables de tensio-actifs non ioniques comprenant un agent regulant la viscosite - Google Patents
Emulsions aqueuses stables de tensio-actifs non ioniques comprenant un agent regulant la viscosite Download PDFInfo
- Publication number
- WO1994011099A1 WO1994011099A1 PCT/US1993/010444 US9310444W WO9411099A1 WO 1994011099 A1 WO1994011099 A1 WO 1994011099A1 US 9310444 W US9310444 W US 9310444W WO 9411099 A1 WO9411099 A1 WO 9411099A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrophobic
- nonionic surfactant
- hydrophilic
- ethylenediamine
- disuccinic acid
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to cleaning compositions. More particularly, the cleaning compositions according to the present invention are stable aqueous emulsions of nonionic surfactants which comprise a viscosity control system.
- cleaning compositions have been described in the art. For instance, in co-pending European Patent Application EP 92870188.7, a particular type of cleaning compositions is described which are aqueous emulsions of a nonionic surfactant system.- Such emulsions find a preferred application in the formulation of bleaching compositions comprising hydrogen peroxide or water soluble source thereof and a liquid hydrophobic bleach activator, or any other hydrophobic ingredient which needs to be separated from hydrogen peroxide.
- such emulsions can be used to formulate products which do not contain hydrogen peroxide.
- such emulsions can be useful because they allow to keep a given hydrophobic ingredient separate from the aqueous phase, with which said hydrophobic ingredient could react, e.g., by hydrolysis.
- cleaning compositions be more or less viscous. Indeed, viscous compositions do not run like thin liquids, and their pouring, dispensing, i.e. their overall handling is therefore easier to control. This aspect is particularly important when cleaning compositions are used to clean hard surfaces, especially on inclined or vertical surfaces such as toilet bowls, or in the context of laundry. In those instances, the cleaning compositions must be thick enough for a controlled application onto fabrics, and for a good cling onto surfaces.
- thickening compounds are available for this purpose.
- thickening compounds it is meant herein compounds whose sole function is to thicken the compositions.
- Such compounds typically polymers, are however rather undesirable for a variety of reasons. Indeed, they can significantly increase formula cost without participating to the overall cleaning performance, they may involve processing issues, they may affect product stability, particularly in extreme acidic conditions, and they may affect the cleaning performance of the compositions.
- Another advantage of the present invention is that it is only required to use a very small amount of ethylenediamine-N,N'-disuccinic acid in order to obtain the desired effect, which makes the present invention particularly cost-efficient.
- ethylenediamine-N,N'-disuccinic acid also acts as a builder in the compositions of the present invention.
- ethylenediamine-N,N'-disuccinic plays has a dual function in the compositions of the present invention.
- Another advantage of the present invention is that it allows for the formulation of compositions which are thick and pseudoplastic, i.e. which are less viscous at higher shear stresses.
- Pseudoplasticity compositions achieve the multiple and somewhat contradictory objects of being easy to dispense, i.e. rather less viscous, and providing good cling onto surfaces, i.e. rather more viscous.
- Yet another advantage of the present invention is that ethylenediamine-N,N'-disuccinic acid has been found to provide additional stability to the preferred compositions herein which may comprise hydrogen peroxide as an optional but preferred compound. Yet another advantage of the present invention is that it allows to achieve a given viscosity target with a lower surfactant level, compared to a composition without ethylenediamine-N,N'-disuccinic acid.
- the present invention is a stable aqueous emulsion comprising a hydrophilic nonionic surfactant and a hydrophobic nonionic surfactant, said stable aqueous emulsion further comprising a viscosity-building amount of ethylenediamine-N,N'-disuccinic acid.
- compositions according to the present invention are stable aqueous emulsions of nonionic surfactants.
- stable emulsion it is meant an emulsion which does not substantially separate into distinct layers, upon standing for at least two weeks at 20 °C, preferably at least six months.
- compositions according to the present invention are aqueous. Accordingly, the compositions according to the present invention comprise from 10% to 95% by weight of the total composition of water, preferably from 30% to 90%, most preferably from 60% to 85%. Deionized water is preferably used.
- compositions according to the present invention are emulsions of nonionic surfactants.
- Said emulsions of nonionic surfactants comprise at least two nonionic surfactants.
- said two nonionic surfactants must have. different HLB values (hydrophilic lipophilic balance) , and preferably the difference in value of the HLBs of said two surfactants is at least 1, preferably at least 3.
- nonionic surfactant with an HLB above 11 (herein referred to as hydrophilic nonionic surfactant)
- nonionic surfactant with an HLB below 10 herein referred to as hydrophobic nonionic surfactant
- Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols. Indeed, a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values (hydrophilic lipophilic balance) .
- the HLB values of such alkoxylated nonionic surfactants depend essentially on the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a higher degree of alkoxylation, while hydrophobic surfactants tend to have a lower degree of alkoxylation.
- Surfactants catalogs are available which list a number of surfactants including nonionics, together with their respective HLB values.
- compositions according to the present invention comprise from 2 % to 70 % by weight of the total composition of said hydrophilic and hydrophobic nonionic surfactants, preferably from 3 % to 40 %, most preferably from 4 % to 30 %.
- compositions according to the present invention may further comprise other nonionic surfactants which should however not significantly alter the weighted average HLB value of the overall composition.
- the compositions according to the present invention further comprise as an essential element a viscosity-building amount of ethylenediamine-N,N' -disuccinic acid.
- viscosity-building it is meant herein any amount of ethylenediamine-N, * -disuccinic acid in a given composition which will provide an increase in viscosity compared to the same composition without ethylenediamine-N,N' -disuccinic acid, while maintaining acceptable stability.
- compositions herein are not limited to any specific viscosity, and depending on the exact use envisioned, various viscosities may be achieved.
- the addition of the dipicolinic acid or derivatives thereof to a given composition may produce a viscosity increase or decrease of from 5 cps to 2000 cps, preferably from 50 cps to 1000 cps, at a given shear rate, compared to the same composition without dipicolinic acid or derivatives thereof.
- the decrease or increase is greater when measured at low shear rates (e.g. 12 rpm) .
- compositions according to the present invention may comprise from 0.01 % to 10 % by weight of the total composition of ethylenediamine-N,N'-disuccinic acid, preferably from 0.01 % to 1 %.
- Ethylenediamine-N,N* -disuccinic acid can be synthesised, for example, from readily available, inexpensive starting materials such as maleic anhydride and ethylenediamine as follows. O / ⁇
- the [S,S] isomer of ethylenediamine-N,N'-disuccinic acid can be synthesised from L-aspartic acid and 1,2-dibromoethane, as follows.
- Ethylenediamine-N,N'-disuccinic acid can be used in the compositions of the present invention in its acid form or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
- Preferred ethylenediamine-N,N'-disuccinic acid compounds for inclusion in the present compositions are the free acid form and the sodium or magnesium salt thereof.
- Examples of such preferred sodium salts of ethylenediamine-N,N•- disuccinic acid include Mg ethylenediamine-N,N'-disuccinic acid and Mg 2 ethylenediamine-N, ' -disuccinic acid.
- the magnesium complexes are the most preferred for inclusion in compositions according to the invention.
- These complexes may be added to the compositions as such, or they may be formed during the process for making the composition by the reaction of an inert magnesium salt such as MgCl2 or Mg S0 4 with an ethylenediamine-N,N * -disuccinic acid compound added as either the acid, or as a salt or complex.
- an inert magnesium salt such as MgCl2 or Mg S0 4
- an ethylenediamine-N,N * -disuccinic acid compound added as either the acid, or as a salt or complex.
- the ethylenediamine-N,N'-disuccinic acid compound is added in the making process, together with the inert magnesium salt, it is preferred that the molar ratio of magnesium to ethylenediamine-N;N'-disuccinic acid should be greater than 1:1, preferably greater than 3:1, to ensure formation of the desired magnesium complexes.
- the pH of the formulation influences its stability.
- bleaching ingredients being optional but preferred ingredients of the compositions herein, it is of course necessary, for chemical stability purposes to formulate the compositions herein with bleaches at a pH as is of from 0 to 6, preferably of from 0.5 to 5.
- the pH of the can be trimmed by all means available to the man skilled in the art.
- compositions according to the present invention comprise bleaches, i.e. hydrogen peroxide or water-soluble sources thereof.
- Suitable water-soluble sources of hydrogen peroxide include perborate, percarbonate and persilicate salts.
- Hydrogen peroxide is most preferred to be used in the compositions according to the present invention.
- the compositions according to the present invention comprise from 0.5% to 20% by weight of the total composition of hydrogen peroxide, preferably from 2% to 15%, most preferably from 3% to 10%.
- compositions according to the present invention may further comprise a bleach activator as an optional ingredient.
- bleach activator it is meant herein any compound which reacts with hydrogen peroxide to form a peracid.
- Suitable bleach activators for use herein typically belong to the class of esters, amides, imides, or anhydrides.
- a particular family of bleach activators of interest in the present invention were disclosed in applicant's co-pending European patent application No 91870207.7. Particularly preferred in that family is acetyl triethyl citrate which was also disclosed in the context of bar soaps in FR 2 362 210.
- Acetyl triethyl citrate has the advantages that it is environmentally friendly as it eventually degrades into citric acid and alcohol.
- acetyl triethyl citrate has a good hydrolytical stability in the product upon storage and it is an efficient bleach activator.
- the term bleach activator includes mixtures of bleach activators.
- the nonionic surfactant system to be chosen to emulsify said bleach activator depends on the HLB value of said bleach activator. Accordingly, a suitable way to proceed is to determine the HLB value of the hydrophobic liquid ingredient (bleach activator) , then select both the hydrophobic nonionic surfactants which have HLB values below said HLB value of said hydrophobic liquid ingredient and the hydrophilic nonionic surfactants which have HLB values above said HLB value of said hydrophobic liquid ingredient, wherein the difference in the HLB values of said hydrophobic and hydrophilic nonionic surfactants is preferably at least 3.
- the emulsifying system meets the equation:
- X refers to the hydrophobic liquid ingredient to emulsify
- A refers to one of said nonionic surfactants (hydrophilic or hydrophobic)
- B refers to the other said nonionic surfactant (hydrophilic or hydrophobic) .
- an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with an HLB from l to 10, and a hydrophilic nonionic surfactant with an HLB of above 11.
- a particularly suitable system comprises a hydrophobic nonionic surfactant with an HLB of 6, for instance a Dobanol @ 23-2 and a hydrophilic nonionic surfactant with an HLB of 15, for instance a Dobanol @ 91-10.
- Another suitable nonionic surfactant system comprises a Dobanol-*-* 23-6.5 (HLB about 12) and a Dobanol @ 23 (HLB below 6). All these Dobanol surfactants are commercially available from Shell.
- compositions according to the present invention may further comprise the usual optional ingredients such as perfumes, dyes, optical brighteners, builders and chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents and the like.
- compositions according to the present invention are particularly useful as laundry pretreaters, i.e compositions which are dispensed and left to act onto fabrics before they are washed, or as laundry additives to be used together with detergents to boost their performance, or as dishwashing compositions to be used either in the dishwashing machines or by hand, or as hard surface cleaners, or as toilet bowl cleaners, or as carpet cleaners to be used either by direct application onto the carpets or in carpet cleaning machines.
- the present invention further encompasses a process for the manufacture of the composition described herein.
- the process according to the present invention comprises at least three steps:
- a hydrophobic mixture which comprises said hydrophobic nonionic surfactant, ethylenediamine-N,N'-disuccinic acid, together with other, optional, hydrophobic ingredients which are to be formulated in the composition, such as perfumes, solvents, enzymes, bleach activators and polymers.
- a hydrophilic mixture which comprises at least said water, and said hydrophilic nonionic surfactant.
- Said hydrophilic mixture preferably further comprises other hydrophilic ingredients which are to be formulated in the composition such as dyes, optical brighteners, builders, chelants, hydrogen peroxide and buffering agents.
- first and said second steps can be performed in any order, i.e second step first is also suitable.
- said hydrophobic mixture and said hydrophilic mixture are mixed together.
- compositions are made which comprise the listed ingredients in the listed proportions (weigh %) .
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Colloid Chemistry (AREA)
Abstract
Emulsions aqueuses stables renfermant des tensio-actifs non ioniques hydrophobes et hydrophiles, et un acide éthylènediamine -N,N'-discuccinique. L'acide éthylènediamine-N,N'-disuccinique renforce la viscosité desdites émulsions.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU55891/94A AU5589194A (en) | 1992-11-16 | 1993-10-29 | Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP92870188A EP0598170B1 (fr) | 1992-11-16 | 1992-11-16 | Compositions de nettoyage et de blanchiment |
EP92870188.7 | 1992-11-16 | ||
EP93870104A EP0629690B1 (fr) | 1993-06-09 | 1993-06-09 | Emulsions aqueuses stables d'agents tensioactifs non-ioniques |
SG1996008330A SG55157A1 (en) | 1993-06-09 | 1993-06-09 | Stable aqueous emulsions of nonionic surfactants |
SG1996002630A SG52309A1 (en) | 1993-06-09 | 1993-06-09 | Stable aqueous emulsions of nonionic surfactants |
EP93870103.4 | 1993-06-09 | ||
EP93870104.2 | 1993-06-09 | ||
EP93870103A EP0629691B1 (fr) | 1993-06-09 | 1993-06-09 | Emulsions aqueuses stables d'agents tensioactifs non-ioniques |
EP93870134A EP0598693B1 (fr) | 1992-11-16 | 1993-07-12 | Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrÔle de la viscosité |
EP93870134.9 | 1993-07-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994011099A1 true WO1994011099A1 (fr) | 1994-05-26 |
Family
ID=27545649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/010444 WO1994011099A1 (fr) | 1992-11-16 | 1993-10-29 | Emulsions aqueuses stables de tensio-actifs non ioniques comprenant un agent regulant la viscosite |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0598693B1 (fr) |
AT (1) | ATE174955T1 (fr) |
AU (1) | AU5589194A (fr) |
DE (1) | DE69322744T2 (fr) |
ES (1) | ES2125322T3 (fr) |
WO (1) | WO1994011099A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997008288A1 (fr) * | 1995-08-30 | 1997-03-06 | The Dow Chemical Company | Chelatants degradables derives de l'acide succinique, leurs utilisations et compositions |
EP0791095A1 (fr) * | 1994-11-10 | 1997-08-27 | The Procter & Gamble Company | Procede de nettoyage de moquette |
US5733858A (en) * | 1995-08-30 | 1998-03-31 | The Dow Chemical Company | Succinic acid derivative degradable chelants, uses and compositions thererof |
US5905065A (en) * | 1995-06-27 | 1999-05-18 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
US5928384A (en) * | 1994-11-10 | 1999-07-27 | The Procter & Gamble Company | Method of cleaning carpets |
EP1370224B2 (fr) † | 2001-03-20 | 2013-08-14 | The Procter & Gamble Company | Compositions convenant pour le traitement des cheveux comprenant des agents chelatants, et procede pour reduire la deterioration des cheveux par oxydation |
WO2015174567A1 (fr) * | 2014-05-15 | 2015-11-19 | 코오롱인더스트리 주식회사 | Polyimide et film l'utilisant |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996006908A1 (fr) * | 1994-08-26 | 1996-03-07 | The Procter & Gamble Company | Ethylenediamine disuccinate utilise comme detergent |
EP0779357A1 (fr) * | 1995-12-16 | 1997-06-18 | The Procter & Gamble Company | Emulsions stables contenant un ingrédient hydrophobe liquide |
EP0993507A1 (fr) * | 1997-06-27 | 2000-04-19 | The Procter & Gamble Company | Compositions detergentes liquides non aqueuses contenant des particules enzymatiques |
EP0906950A1 (fr) * | 1997-10-03 | 1999-04-07 | The Procter & Gamble Company | Compositions contenant des agents de blanchiment péroxydés comprenant un système d'agent chélatant particulier |
DE19961659A1 (de) * | 1999-12-21 | 2001-07-12 | Henkel Kgaa | Mittel zur Behandlung von Substraten |
EP1233055A1 (fr) * | 2001-02-15 | 2002-08-21 | Givaudan SA | Composition de blanchissement |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4704233A (en) * | 1986-11-10 | 1987-11-03 | The Procter & Gamble Company | Detergent compositions containing ethylenediamine-N,N'-disuccinic acid |
EP0386566A1 (fr) * | 1989-03-06 | 1990-09-12 | Henkel Kommanditgesellschaft auf Aktien | Suspension d'un agent de blanchissement |
AU1060992A (en) * | 1991-02-01 | 1992-08-06 | Hoechst Aktiengesellschaft | Aqueous suspensions of peroxycarboxylic acids |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE163037T1 (de) * | 1992-11-16 | 1998-02-15 | Procter & Gamble | Reinigungs- und bleichmittelzusammensetzungen |
SG55157A1 (en) * | 1993-06-09 | 1998-12-21 | Procter & Gamble | Stable aqueous emulsions of nonionic surfactants |
ES2137245T3 (es) * | 1993-06-09 | 1999-12-16 | Procter & Gamble | Emulsiones acuosas estables de tensioactivos no ionicos. |
-
1993
- 1993-07-12 DE DE69322744T patent/DE69322744T2/de not_active Expired - Fee Related
- 1993-07-12 ES ES93870134T patent/ES2125322T3/es not_active Expired - Lifetime
- 1993-07-12 EP EP93870134A patent/EP0598693B1/fr not_active Expired - Lifetime
- 1993-07-12 AT AT93870134T patent/ATE174955T1/de not_active IP Right Cessation
- 1993-10-29 AU AU55891/94A patent/AU5589194A/en not_active Abandoned
- 1993-10-29 WO PCT/US1993/010444 patent/WO1994011099A1/fr active Search and Examination
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4704233A (en) * | 1986-11-10 | 1987-11-03 | The Procter & Gamble Company | Detergent compositions containing ethylenediamine-N,N'-disuccinic acid |
EP0386566A1 (fr) * | 1989-03-06 | 1990-09-12 | Henkel Kommanditgesellschaft auf Aktien | Suspension d'un agent de blanchissement |
AU1060992A (en) * | 1991-02-01 | 1992-08-06 | Hoechst Aktiengesellschaft | Aqueous suspensions of peroxycarboxylic acids |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0791095A1 (fr) * | 1994-11-10 | 1997-08-27 | The Procter & Gamble Company | Procede de nettoyage de moquette |
EP0791095A4 (fr) * | 1994-11-10 | 1997-10-15 | Procter & Gamble | Procede de nettoyage de moquette |
US5928384A (en) * | 1994-11-10 | 1999-07-27 | The Procter & Gamble Company | Method of cleaning carpets |
US5905065A (en) * | 1995-06-27 | 1999-05-18 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
WO1997008288A1 (fr) * | 1995-08-30 | 1997-03-06 | The Dow Chemical Company | Chelatants degradables derives de l'acide succinique, leurs utilisations et compositions |
US5733858A (en) * | 1995-08-30 | 1998-03-31 | The Dow Chemical Company | Succinic acid derivative degradable chelants, uses and compositions thererof |
US5846925A (en) * | 1995-08-30 | 1998-12-08 | The Dow Chemical Company | Succinic acid derivative degradable chelants, uses and compositions thereof |
EP1370224B2 (fr) † | 2001-03-20 | 2013-08-14 | The Procter & Gamble Company | Compositions convenant pour le traitement des cheveux comprenant des agents chelatants, et procede pour reduire la deterioration des cheveux par oxydation |
WO2015174567A1 (fr) * | 2014-05-15 | 2015-11-19 | 코오롱인더스트리 주식회사 | Polyimide et film l'utilisant |
KR101615431B1 (ko) | 2014-05-15 | 2016-04-25 | 코오롱인더스트리 주식회사 | 폴리이미드 및 이를 이용한 필름 |
Also Published As
Publication number | Publication date |
---|---|
DE69322744D1 (de) | 1999-02-04 |
AU5589194A (en) | 1994-06-08 |
EP0598693B1 (fr) | 1998-12-23 |
ATE174955T1 (de) | 1999-01-15 |
ES2125322T3 (es) | 1999-03-01 |
EP0598693A1 (fr) | 1994-05-25 |
DE69322744T2 (de) | 1999-07-22 |
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